JPS6053508A - Polymer of sulfonated dicyclopentadiene - Google Patents

Abstract

PURPOSE:The titled polymer, obtained by polymerizing a sulfonated dicyclopentadiene expressed by a specific formula, and having excellent surface activity and particularly cement dispersing action. CONSTITUTION:A polymer of a sulfonated dicyclopentadiene obtained by polymerizing a sulfonated dicyclopentadiene, expressed by the formula (M is H, alkali metal, alkaline earth metal, ammonium or amine; m is 2 when M is alkaline earth metal, and 1 when M is other than the alkaline earth metal; n is the polymerization degree), and prepared by using preferably 0.1-10mol, based on 1mol dicyclopentadiene, acid alkali metal sulfite in the presence of an acid compound catalyst, e.g. sulfuric acid. The molecular weight of the above-mentioned polymer is preferably 500-80,000, and particularly 3,500-50,000 in using as a cement dispersing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention Vi1 relates to a polymer or copolymer of a sulfonated dicyclopentadiene containing a sulfonic acid group.

BACKGROUND OF THE INVENTION In general, organic compounds such as sulfonic acids and their derivatives are strong acids such as sulfuric acid, comparable to sulfuric acid, and are widely used industrially due to their properties. Moreover, since the salt is water-soluble, it is of great importance as a surfactant for organic or inorganic materials.

However, most of the sulfonated compounds conventionally synthesized are aromatic or aliphatic sulfonated compounds.

Few examples of sulfonated alicyclic compounds are known.

Moreover, the polymer or copolymer having a sulfonic acid group in the dicyclopentadiene skeleton of the present invention is not known at all.

Purpose of the Invention The present inventors conducted extensive studies to obtain a polymer or copolymer of a sulfonated product having a dicyclopentadiene skeleton. 1 can be polymerized,
It was discovered that the polymer of sulfonated compound of 200% has extremely excellent surface activity, and that it has an excellent cement dispersion effect, leading to the present invention.

The constitution of the invention, that is, the present invention provides a polymer or copolymer of an acid or salt of a dicyclopentadiene sulfonating agent represented by the following general formula.

However, M in the formula is a hydrogen atom or an alkali metal atom.

Represents an alkaline earth metal atom, ammonium group or amine, and 1M is an alkaline earth metal atom.
When 8( is other than an alkaline earth metal atom, mf is expressed as 1, and nPi polymerization degree is expressed as l.
It's a confusing number.

The configuration τ of the present invention will be explained in detail below.

An example of M in the above formula (1) VC is as follows.

Examples of alkali metals: sodium and potassium Examples of alkaline earth metals: calcium and magnesium amines V Examples: alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, butylamine, dibutylamine, tributylamine ; Polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; Heterocyclic amines such as morpholine and piperidine.

The above M can be mutually exchanged with another type of M by one type of ion exchange technique or 1zJl neutralization reaction. It can be freely converted among the acid type, alkali metal salt type, alkaline earth metal salt type, ammonium salt type, and amine salt type.

Raw Materials Dicyclopentadiene used in the present invention may contain impurities such as other hydrocarbons and water, as long as they do not interfere with one reaction. Further, even if alkyl-substituted dicyclopentadiene such as methyldicyclopentadiene is mixed, there is no particular problem in the present invention. The method for sulfonating dicyclopentadiene is Gilbar) (H,1
3, G11bert) in his book ``Sulfonation and Related Reactions''('5ulfona-tion and Relat
edReactiorr') Interscience
Publishers Inc. (1965). It was a cabinet. Charles J. Norton et al. in The Journal of Organic Chemistry (
The Journal of Organic
4158 (1968), sulfonated products can also be obtained by the addition reaction of sulfites to unsaturated bonds. As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkaline ends are usually used alone or in mixtures. The fit of these sulfonating agents.

It varies depending on the degree of sulfonation required, and although it cannot be determined generally, it is usually used in a ratio of 0.1 to 10 molecules per molecule of dicyclopentadiene.

Although the use of a catalyst is not necessarily required in this sulfonation reaction, the reaction time can usually be shortened by using a catalyst such as an inorganic oxidizing agent. Examples of inorganic oxidizing agents include nitrates, nitrites, chlorates, etc. Nitrates are preferred for F.

Furthermore, an appropriate solvent may be used to allow one reaction to proceed uniformly and smoothly. Examples of solvents that can be used advantageously are water and methyl alcohol.

Ethyl alcohol, flobyl alcohol, inflobil alcohol, methyl alcohol m[3Mf Lower alcohols such as methyl alcohol, lower glycols, ketones 1. Examples include ethers and esters. Two or more of these solvents can be used in combination as appropriate. Of these, mixed solvents of lower alcohols and water, especially propyl alcohol and water, are recommended as excellent solvents.

The reaction accuracy in sulfone ratio reaction is usually 50-200℃
, preferably 170 to 150°C, more preferably 9
The temperature is 0 to 120°C, and it can also be carried out in a chair tL under pressure or pressure. It also suppresses the progress of side reactions,
In order to reduce the formation of unnecessary inorganic layers, the pH of the 1 anti-L6 system is
is usually 2-9. It is desirable to keep it between 5 and 7.

In this way, unreacted c') a-like compounds can be separated by extraction with water. As a result of this operation, unreacted inorganic salts present in the aqueous phase can be separated by, for example, crystallization.

The sulfone ratio that can be suppressed in this way has one molecule of sulfonic acid group per molecule, and the main product is one in which sulfone 7s is added to norbornene. (See Japanese Patent Application No. 57-174400.) Production method The polymer or Yj copolymer of the present invention is prepared by mixing dicyclopentadiene having a sulfonic acid group with a melon in the presence of, for example, an acidic compound catalyst. can get.

An example of the method for producing the polymer or copolymer of the present invention will be shown below.

(M gold catalyst) Acidic catalytic acid catalysts are used as catalysts for polymerization.

For example, sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its wood, salt fheal aluminum, aluminum bromide,
Lewis acids such as tin tetrachloride, zinc chloride, and Mitaka titanium or organic protonic acids can be mentioned.

(Claw bed operation) In the presence of such a method medium, a sulfonated product of synchropentadiene, or a polymerizable monomer is usually reacted at a reaction temperature of -20 to 300°C, preferably 80 to 80°C.
A polymer is obtained by carrying out a polymerization reaction at 180° C. for several hours to several tens of hours. In this polymerization reaction, a polymerization reaction solvent can be used to smoothly carry out the 1ri1 reaction,
As the solvent for the polymerization reaction, any solvent such as polar solvents such as water, hydrocarbons, and non-loginated hydrocarbons can be used as long as it does not interfere with the polymerization reaction.

In order to adjust the surface activity of the copolymerized monomer polymer, HLB (surfactant Characteristics) can also be changed.

Examples of copolymerizable monomers include aliphatic, alicyclic, and aromatic hydrocarbons having olefinic double bonds, unsaturated amides, unsaturated alcohols, and unsaturated esters.

One or more of unsaturated nitriles, unsaturated carzenic acids and esters thereof, unsaturated sulfo/V and esters thereof, etc. can be used in any proportion.

However, if the copolymer of the present invention is used as a cement dispersant,
In order to keep f'izp gas entrainment low when used as a copolymer, the content of sulfonated compounds in the copolymer of the present invention is set to be at least Vi 50%, preferably at least 70%, and more preferably at least Y'i 90%.

Molecular Weight The weight average molecular weight of the polymer or copolymer of the present invention is 5
00-80. OQ O, but reaction conditions.

In particular, it can be changed as appropriate depending on the type and amount of the acidic compound catalyst, the type and location of the solvent, or the reaction temperature and reaction time.

When the sulfonated polymer or copolymer of the present invention is used as a dispersant for cement, the monomer average molecular weight is 50.
Vi20 is preferably 0 or more, more preferably Vi20
00 or more, most preferably 3500 to 50.000.

Applications Since the sulfonated polymer or copolymer of the present invention is as described above, it has a strong surface-active effect, as will be understood from the examples described below, and therefore can be used as an organic material. Alternatively, it is extremely useful as a surfactant for inorganic materials, and can be widely used as, for example, an emulsifier, a dispersant, a wetting agent, a cleaning agent, and a smoothing agent.

Furthermore, the sulfonated polymer spanning copolymer of the present invention is
Particularly useful as a dispersant for cement.

In this case, as will be understood from the explanation of the examples below, it is possible to significantly improve the dispersibility of cement in water, and therefore, it is possible to obtain a water reduction effect in the cement construction method. Since there is little air entrainment, it is possible to obtain concrete with high strength.

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

The weight average molecule t stated in the license fee is based on the results measured by gel/glue mission chromatography (GPO) using the WILt line created using several types of polystyrene sulfonic acids with different numbers of molecules as standard substances. This is the converted value.

The total eluate was dissolved in a mixture of acetonitrile and 0.5N Na280m aqueous solution at a weight ratio of 3=7.The column was a TSK-GEL manufactured by Toyo Soda Co., Ltd.
G3000SW and TSK-GEL G2000SW were connected in series, and the measurement was performed using a UV detector.

From the obtained GPO chart.

Σ((molecular weight) x (area)) total area was calculated and the weight average molecular weight was determined.

Example 1 In a stainless steel autoclave with a capacity of 301, equipped with a stirring device and a d-shaped needle, 3000 g of dicyclopentadiene was added.
f, sodium bisulfite 188B? .

Potassium nitrate (91.7 f), isozorobyl alcohol (12 t), and distilled water (3,000 P) were added, and the internal pressure in the autoclave was brought to 1.7 f at room temperature. After nitrogen was supplied until the pressure reached 0 kg/cn (gauge pressure), the valve was sealed and the reaction was carried out at 110° C. for 5 hours while mixing under -C1 strong stirring. After that, it was allowed to cool to room temperature, and most of the isopropyl alcohol was removed by distillation.

Distilled water and petroleum ether were added and thoroughly mixed, and the separated petroleum ether layer and precipitate were removed, and the resulting aqueous layer was concentrated and distilled to dryness. This 11 was dissolved in glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated by centrifugation. By concentrating the obtained acetic acid solubles, a white solid 2
I got 8009. Next, 5, Ot equipped with a stirring device
In a glass-lined autoclave, add the above sulfonated compound A for 1.5 hours, #21.0kr of sulfur, and 0.5kr of water.
G1 preparation.

A polymerization reaction was carried out at 120° C. for 6 hours. After the reaction was completed, liming was performed with OaOOg to remove sulfuric acid, and the solid content obtained was 1.4 kg.

The molecular weight distribution of this product is shown in Figure 3. The weight average molecular JIk calculated from this was 8.850.

The In chart of this product is shown in Figure 1, and it was found that it had a sulfonic acid group, and the surface tension of a 4-layer aqueous solution of this product was as high as 69.7, dyn^.

Next, the solid high-resolution 13C-NMa spectrum of this product is shown in FIG. 2, and the structure of the obtained polymer was identified to be mainly O 2 from the absorption intensity ratio and chemical shift position.

Example 2 In Example 1, a polymer was obtained at a polymerization temperature of 13°C (1°C).The inspection average molecular t of this product was 13,400, and a spectrum similar to that shown in Figures 1 and 2 was obtained. The surface tension of a 4% by weight aqueous solution of this product was 70.6 dyn.

Example 3 A polymer was obtained in Example 1 except that the polymerization temperature was set to '2tou°C. The weight average molecule Jilk of this is 2.21)0
, and the surface tension Lj of the 4-weight polyhydric bath liquid is 64.8 dY.
It was 71m. Furthermore, this item's IR and "
The O-NMR spectrum was very similar to FIGS. 1 and 2.

Example 4 An experiment was conducted in the same manner as in Example 1 except that the polymerization reaction temperature was changed to 140°C, and one polymer was obtained with a weight of 1.3. It was 000. Since the technical chart of this polymer was exactly the same as that shown in FIG. 1, it was confirmed that it was an M combination having the same structure as the heavy metal body of Example 10.

Example 5 The polymer 242 obtained in Example 1 was added to 1000 g of water.
'? It was then layered in a strongly acidic cation exchange resin io, oo y that had been converted into a brewer, and after being allowed to stand day and night, the resin was removed by filtration and the F solution was dried to dryness. The solid content obtained was 212. Elemental analysis of this material revealed that it was 54.8% carbon.

The theoretical values of the polymer of the present invention are 7.3% hydrogen, 15.2% sulfur, and 22.7% oxygen. 2% (after all, there was good agreement).

Next, this product was subjected to phase titration with NaOH''C, and was neutralized with an equivalent amount of NaOH.From these results, the polymer after cation exchange treatment was determined to have the general formula of Komaei. , M = 11, and the neutralization wave μM=NaK is converted to tL/L.

Example 6 Example 5 O acid fJl (Dfg combined f K OH, Oa
(OH)*, NHj water, and monoethanolamine were used to neutralize the polymer. separated. This is what I'm talking about.

Oa, NU (monoethanolamine salt c/) polymer. The Gl['O,I analysis of these polymers was conducted using the actual
[F] was almost the same as Example 1°. In addition, elemental analysis of these polymers showed the binding, K, Cal/2. NI44
, monoethanolamine etc. to the sulfonic acid group.
It was confirmed that 1C1 money was included.

Example of Use 22 of each of samples 1 to 3 obtained in 2ilT1 rows 1 to 3V were added to 567 liters of distilled water and dissolved to prepare a total of 3 types of aqueous liquids. PC of each aqueous solution
ttj Sales Portland Cement (manufactured by Chichibu Cement Co., Ltd.) 2
After adding 00 ri and kneading by hand for 3 minutes, the inner d product was 9819.
Using cc Noah o-, near-in, J13 几5201 K-C-F"-rlIf7-11, the results are shown in the following table.

Sample 1 ~; Although it does not include the sea urchin j'tshi) 1 above and 1 [processed like IJ, C flow pupil is di (I set to 7, slightly in order of 110) It was.

In view of the effectiveness of the invention, the sulfonated polymer of the present invention has an excellent surfactant action, and as shown in the examples of use, it does not disintegrate. 1. The sulfonated compound of the present invention (i) used as a dispersant for agglomerated electrocement has an extremely excellent dispersion effect of cement in water.

[Brief explanation of the drawing]

Fig. 1 is a υI spectral chart of the polymer of the present invention, Fig. 2 is an O-NM spectrum diagram of the polymer of the present invention, and Fig. 3 is a GOP chart of the polymer of the present invention. Person: Japan Synthetic Rubber Co., Ltd. Representative Patent Attorney Minoru Isaka

Claims (1)

[Claims] A polymer of a sulfonated dicyclopentadiene represented by the following general formula. However, M in the formula is a hydrogen atom or an alkali metal atom. It represents an alkaline earth metal atom, an ammonium group or a mineral amine, and when 1M is an alkaline earth metal atom, m is 2.
When 1M is an atom other than an alkaline earth metal atom, 7 yo mμlk is &. is a number representing the degree of polymerization.